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The ability to predict accurately the thermal conversion of complex carbonaceous materials under a wide range of heating rates and temperatures is of value in both petroleum exploration and refining operations. Modeling the thermal cracking of kerogen and coal under basinal heating conditions improves the pre-drill prediction of oil and gas yields and quality, thereby ultimately lowering exploration risk. Modeling the chemical structure and reactivity of asphaltenes from petroleum residues enables prediction of coke formation and properties in refinery processes, thereby lowering operating cost. Previous compositional yield models based on laboratory yield measurements have been developed for specific materials, such as isolated coals and kerogens, but extrapolation to predict oil and gas generation during geologic burial is problematic. Furthermore, models based on a few reference carbonaceous materials may not simulate varying compositions of kerogen and residues seen in nature. We have developed a method to calculate the amounts and composition of products resulting from the thermal decomposition of a solid complex carbonaceous material. This procedure provides a means of using laboratory measurements of complex carbonaceous solids to construct a representative model of its chemical structure (CS) that is then coupled with elementary reaction pathways to predict the chemical yield (CY) upon thermal decomposition. Data from elemental analysis (C, H, N, O, S), solid state 13C NMR, X-ray photoelectron spectroscopy (XPS), sulfur X-ray absorption structure spectroscopy (XANES), and pyrolysis-gas chromatography (GC) are used to constrain the construction of core molecular structures representative of the complex carbonaceous material. These core structures are expanded stochastically to describe large macromolecules (>104 cores with ∼106 atoms) with bulk properties that match the experimental results. Gas, liquid and solid product yields, resulting from thermal decomposition, are calculated by identifying reactive functional groups within the CS stochastic ensemble and imposing a reaction network constrained by fundamental thermodynamics and kinetics. An expulsion model is added to the decomposition model to calculate the chemical products in open and closed systems. Product yields may then be predicted under a wide range of time–temperature conditions used in rapid laboratory pyrolysis experiments, refinery processes, or geologic maturation.

The identification and allocation of multiple hydrocarbon sources in marine sediments is best achieved using an holistic approach. Total organic carbon (TOC) is one important tool that can constrain the contributions of specific sources and rule out incorrect source allocations in cases where inputs are dominated by fossil organic carbon. In a study of the benthic sediments from Prince William Sound (PWS) and the Gulf of Alaska (GOA), we find excellent agreement between measured TOC and TOC calculated from hydrocarbon fingerprint matches of polycyclic aromatic hydrocarbons (PAH) and chemical biomarkers. Confirmation by two such independent source indicators (TOC and fingerprint matches) provides evidence that source allocations determined by the fingerprint matches are robust and that the major TOC sources have been correctly identified. Fingerprint matches quantify the hydrocarbon contributions of various sources to the benthic sediments and the degree of hydrocarbon winnowing by waves and currents. TOC contents are then calculated using source allocation results from fingerprint matches and the TOCs of contributing sources. Comparisons of the actual sediment TOC values and those calculated from source allocation support our earlier published findings ( 5 ) that the natural petrogenic hydrocarbon background in sediments in this area comes from eroding Tertiary shales and associated oil seeps along the northern GOA coast and exclude thermally mature area coals from being important contributors to the PWS background due to their high TOC content.

Prince William Sound (PWS), Alaska has an extensive history of human and industrial activity that has produced a complex organic geochemistry record in subtidal sediments of embayments throughout the sound. In addition to contributions from recent oil spills and a regional background of natural petroleum hydrocarbons originating from active hydrocarbon systems in the northern Gulf of Alaska (GOA), pyrogenic and petrogenic PAH were, and continue to be introduced to subtidal sediments at numerous sites of past and present human activities. These sites include villages, fish hatcheries, fish camps and recreational campsites in addition to abandoned settlements, canneries, sawmills, and mines. A holistic approach is used to fingerprint and quantify hydrocarbon contributions from multiple sources in a sediment sample. It involves acquiring a comprehensive understanding of the history of the area to identify potential sources, collection of representative samples, and accurate quantitative analyses of the sourc...

This comment addresses the recent paper by Hostettler et al. proposing a new geochemical refractory PAH index, T/C (the ratio of triaromatic steranes to methyl chrysenes), and using the index to indicate that coal is the main source of the natural petrogenic hydrocarbons in marine sediments in Prince William Sound, Alaska. In response Bench et al. argue that coal is only one of several possibilities, and that measurements of vitrinite/kerogen reflectance, hydrocarbon mass balance calculations, and other molecular indicators including biomarkers demonstrate that coal is not the dominant source. The small sample of data used by Hostettler et al., evidence from vitrinite/kerogen reflectance data, beach coal, mass balance constraints, and the limitations of the T/C index are discussed. Selected molecular parameters in the sediments and in the potential sources of the hydrocarbons background are tabulated.

Polycyclic aromatic hydrocarbons (PAH) are sensitive recorders of past human activities in Prince William Sound, Alaska. In the nearshore subtidal sediments of bays, the fingerprints of the pyrogenic (combustion-derived) PAH record numerous sites of both present and historical human activities including active settlements, fish hatcheries, fish camps and recreational campsites, in addition to abandoned settlements, canneries, sawmills, and mining camps. In instances, there are high levels of PAH attributable to past human activities even though there is little remaining visual evidence of these activities on the shorelines. Forest fires are also an important source of pyrogenic PAH in subtidal sediments at certain time periods and locations and pyrogenic PAH from atmospheric fallout forms part of the regional PAH background. These pyrogenic PAH fingerprints are superimposed on a regional background of natural petroleum hydrocarbons derived from seeps in the eastern Gulf of Alaska. In isolated locations, weathered traces of the Exxon Valdez oil spill were detected as a minor part of the total PAH present from all sources.

This study was conducted to assess the subtidal effects of the Exxon Valdez oil spill in a large embayment in Prince William Sound, AK. A stratified random-sampling design was used to compare stations in an oiled bay, the Bay of Isles, with stations in Drier Bay, a bay that received little impact from the spill. The study included sediment chemistry, benthic ecology, and bioaccumulation elements. Only the results on chemistry of the oil in the bottom sediments are reported here. Analyses of sediment samples revealed four types of polycyclic aromatic hydrocarbons (PAH) in the two bays: (1) Alaska North Slope (ANS) crude oil attributable to the spill, (2) natural oil seep-derived background, (3) pyrogenic, and (4) diagenetic. The Bay of Isles subtidal sediments contained significantly higher levels of weathered ANS-PAH attributable to the spill than did Drier Bay. However, the levels of ANS-PAH in the Bay of Isles were generally lower than those of the petrogenic background PAH naturally present in the sub...

Organic geochemistry played a major role in the environmental assessments conducted following the Exxon Valdez oil spill, which occurred on March 24, 1989, and released about 258,000 bbls (41 million liters) of Alaska North Slope crude oil into Prince William Sound. Geochemical analyses of more than 15,000 sediment, tar, and biological samples and about 5000 water samples provide the largest database yet collected on oil-spill chemistry, and we review the results here. The marine environment of the Sound has a complex background of petrogenic, pyrogenic, and biogenic hydrocarbons from natural and anthropogenic sources. Geochemical evaluation of the fate and effects of the spilled oil required that this oil and its residues be distinguished from the background. A variety of molecular and isotopic techniques were employed to identify various hydrocarbon sources and to distinguish quantitatively among mixed sources in the samples. Although the specific criteria used to distinguish multiple sources in the region affected by the Exxon Valdez spill are not necessarily applicable to all spill situations, the principles that governed their selection are. Distributions of polycyclic aromatic hydrocarbons (PAH) and dibenzothiophenes distinguish Exxon Valdez oil and its weathered residues from background hydrocarbons in benthic sediments. Ratios of C 2 -dibenzothiophene C 2 -phenanthrene and C 3 -dibenzothiophene C 3 -phenanthrene were particularly useful. Carbon isotopes and terpane distributions distinguished Exxon Valdez residues found on shorelines from tars from other sources. Diesel and diesel soot were identified by the absence of alkylated chrysenes and a narrow distribution of n-alkanes, whereas pyrogenic products were distinguished by the dominance of 4- to 6-ring PAH over 2- to 3-ring PAH and by the dominance of non-alkylated over alkylated homologues of each PAH series. The presence of 18α(H)-oleanane in benthic sediments, coupled with its absence in Exxon Valdez oil and its residues, confirm another petrogenic source. Results of geochemical studies suggest that the petrogenic component in the background of benthic sediments is derived from oil seeps in the eastern Gulf of Alaska. In 1990 and 1991, Exxon Valdez residues, generally forming a small increment to the pre-spill background, were found to be only sporadically distributed in some shallow, near shore sediments adjacent to shorelines that had been heavily oiled in 1989. In 1994, occurrences of Exxon Valdez tars on shoreline surfaces were rare, although residues could be found buried in shoreline sediments at some isolated locations along the spill path where they were protected from wave action. Spilled oil residues collected 16 months after the spill were degraded, on average, by nearly 50%. Shoreline residues from sources other than the spill were also identified and are widespread throughout the Sound. These residues include (1) geochemically distinct tars and oils imported from California oil fields to Alaska for fuel and construction purposes prior to the discovery of the Cook Inlet and North Slope oil fields, (2) diesel and diesel soot, and (3) more highly refined products. Of the more than 2700 chemical analyses of biological samples of higher life forms (fish, birds, and mammals) about 150 (6%) indicate recognizable residues of Exxon Valdez oil, which were identified by their distribution of polycyclic aromatic hydrocarbons (PAH). Most of these samples (138) were collected in 1989 and most were associated with external surfaces or the gastrointestinal tract. Rarely do internal tissues or fluids contain recognizable fingerprints of spilled oil. This observation includes samples from marine mammals that were visibly oiled externally. Other hydrocarbon sources, including diesel and a non-petroleum artifact that occurs when concentrations of individual PAH are at or near their method detection limit, are also identified in biological samples.

Advanced hydrocarbon fingerprinting methods and improved analytical methods make possible the quantitative discrimination of the multiple sources of hydrocarbons in the benthic sediments of Prince William Sound (PWS) and the Gulf of Alaska. These methods measure an extensive range of polycyclic aromatic hydrocarbons (PAH) at detection levels that are as much as two orders of magnitude lower than those obtained by standard Environmental Protection Agency methods. Nineteen hundred thirty six subtidal sediment samples collected in the sound and the eastern Gulf of Alaska in 1989, 1990, and 1991 were analyzed. Fingerprint analyses of gas chromatography-mass spectrometry data reveal a natural background of petrogenic and biogenic PAH. Exxon Valdez crude, its weathering products, and diesel fuel refined from Alaska North Slope crude are readily distinguished from the natural seep petroleum background and from each other because of their distinctive PAH distributions. Mixing models were developed to calculate the PAH contributions from each source to each sediment sample. These calculations show that most of the seafloor in PWS contains no detectable hydrocarbons from the Exxon Valdez spill, although elevated concentrations of PAH from seep sources are widespread. In those areas where they were detected, spill hydrocarbons were generally a small increment tomore » the natural petroleum hydrocarbon background. Low levels of Exxon Valdez crude residue were present in 1989 and again in 1990 in nearshore subtidal sediments off some shorelines that had been heavily oiled. By 1991 these crude residues were heavily degraded and even more sporadically distributed. 58 refs., 18 figs., 5 tabs.« less

Major-element, trace-element and isotopic compositions of approximately 1200 basalts ( Mg ( Mg +Fe 2+ ) > 65 ] IAB and MORB are similar, but differ significantly from IPB. In general, IAB do not have higher Al2O3, lower TiO2 or a lack of Fe enrichment compared to primitive MORB but many do have greater K2O contents. Differences in major- and minor-element contents between more evolved IAB and MORB result from the dominance of plagioclase + olivine crystal fractionation in MORB magmas vs. clinopyroxene + olivine controlled fractionation in IAB suites. This difference in crystallization history may be related to the higher PH2O or greater depth of crystallization of IAB magmas compared to those inferred for MORB. IAB are characteristically enriched in large-ion-lithophile (LIL) elements and depleted in high-field-strength ions (e.g., Zr, Nb and Hf) relative to normal MORB (N-type) and IPB. The enrichment of some LIL elements (e.g., Sr, Rb, Ba and Pb) relative to the rare-earth elements in IAB is difficult to explain by simple partial melting alone and suggests a multistage petrogenesis involving an LIL-enriched component. Low abundances of high-field-strength ions in evolved IAB are explicable in terms of fractional crystallization, but the cause for consistently low abundances in primitive IAB remains problematic. Island-arc lavas contain greater concentrations of volatiles and have higher CO 2 H 2 O and Cl/F ratios than either MORB or IPB, suggesting involvement of a slab-derived volatile component. However, this is not consistent with 3 He 4 He data which indicate that only near-trench volcanics have been significantly affected by dehydration of the oceanic crust. Sr-, Nd-, Pb- and O-isotopic data, in conjunction with the trace-element data, clearly indicate that IAB are derived from heterogeneous, LIL-depleted mantle sources most similar to those which give rise to enriched MORB (E-type). The marked shift towards higher 87 Sr 86 Sr in IAB compared to oceanic lavas with similar 143 Nd 144 Nd values cannot be explained simply by the addition of radiogenic Sr from the slab. Variable degrees of contamination from a crustally-derived sedimentary component is consistent with the isotopic and trace-element data from a number of arcs. However, the lack of correlation between LIL/REE ratios and more radiogenic isotopic ratios suggests that this enrichment/contamination process is complex. A multi-stage petrogenetic model involving subducted oceanic crust (± sediments), dehydration/volatile transfer, and partial melting of metasomatized mantle beneath island arcs is considered the most reasonable, although least constrained, method to generate a variety of primitive IAB.

Tholeiitic basalt glasses from the FAMOUS area of the Mid-Atlantic Ridge are among the most primitive basaltic liquids reported from the ocean basins. One of the more primitive of these[Mg/(Mg+Fe2+) = 0.68;Ni= 232ppm;TiO2 = 0.61] glasses (572-1-1) was selected for an experimental investigation. This study found olivine to be the liquidus phase from 1 atm to 10.5 kbar where it is replaced by clinopyroxene. The sequence of appearance of phases at 1 atm pressure is olivine (1268°C), plagioclase (1235°C) and clinopyroxene (1135°C). The sample is multiply saturated at 10.5 kbar with olivine (Fo88), clinopyroxene (Wo32En60Fs9), and orthopyroxene (Wo5En83Fs12). From the 1-atm data we have measured (FeO/MgO) olivine/(FeO*/MgO) liquid (K′D) for olivine-melt pairs equilibrated at 12 temperatures in the range 1268–1205°C.K′D varies from 0.30 at 1205°C to 0.27 at 1268°C. Analysis of high-pressure olivine melt pairs indicates a systematic increase inK′D with pressure. Evaluation of the 1-atm experiments reveals that fractionation of olivine followed by olivine + plagioclase can generate much of the variation in major element chemistry observed in the FAMOUS basalt glasses. However, it cannot account for the entire spectrum of glass compositions — particularly with respect to TiO2 and Na2O. The variations in these components are such as to require different primary liquids. Comparison of clinopyroxene microphenocrysts/xenocrysts found in oceanic tholeiites with experimental clinopyroxenes reveal that the majority of those in the tholeiites may have crystallized from the magma at pressures greater than ∼ 10 kbar and are not accidental xenocrysts. Clinopyroxene fractionation at high pressures may be a viable mechanism for fractionating basaltic magmas. The major and minor element mineral/meltK′d's from our experiments have been used to model the source region residual mineralogy for given percentages of partial melting. These data suggest that ∼20% partial melting of a lherzolite source containing 0–10% clinopyroxene can generate the major and minor element concentrations in the parental magmas of the Project FAMOUS basalt glasses.

Biotite, hornblende and muscovite from 2700 m.y. old rocks in northeastern Minnesota near the contact of the 1150 m.y. Duluth Complex have been analyzed by 40 Ar/ 39 Ar technique to determine whether spectrum ages can be used to distinguish partial loss of radiogenic argon due to a reheating event. Biotite and hornblende give plateau ages comparable to the ordinary K-Ar ages for all samples including those with intermediate ages. Muscovite gives plateau ages for the samples with less than 11% argon loss. An intermediate muscovite with a conventional K-Ar age of 1850 m.y. gives progressively older 40 Ar/ 39 Ar ages for higher temperature fractions. Microprobe analysis reveals no systematic correlation between biotite chemistry and loss of argon in the contact zone. This suggests that the rate-controlling process for the loss of argon from biotite in the contact zone may be volume diffusion or recrystallization without a measurable change in major element composition. Biotites with intermediate ages give plateaus because the rate-controlling processes in the vacuum furnace are related to dehydroxylation and delamination and are unrelated to the process causing loss of argon in the contact zone. The data for the muscovites are not easily interpreted, in part because of the limited number of samples. The hornblende data show a correlation between argon loss and change in major element composition suggesting that recrystallization may be a rate-controlling process for the loss of argon from hornblende in the contact zone. The small number of samples precludes a definitive statement.

Fresh basalt glasses most of which have Mg/(Mg + Fe2+) of 0.66–0.72 from outcrops within 3 km of one other in the rift valley at the Project FAMOUS locality have been analyzed for major, minor and trace elements in order to determine their petrogenesis. Transition metal abundances of the FAMOUS samples are similar to a wide variety of continental and oceanic basalts with high MgO and Ni, all of which show remarkably little variation, with the exception of Cu, Zn and Ti, on a chondrite-normalized plot. Modelling of these data suggests that the mantle beneath both continents and oceans is systematically fractionated relative to chondrites. This fractionation provides a constraint for models of earth formation and subsequent evolution. The abundances of the rare earth and the incompatible elements, Ba, La, Th, U, and Nb, vary by more than a factor of three and the La/Yb and La/Sm ratios vary by factors of 3.1 and 1.6, respectively, in samples with similar, high Mg/(Mg + Fe2+). There is no correlation between the degree of light-REE enrichment and the heavy-REE abundance. Furthermore, the trace element variations do not appear correlated with respect to location in the rift valley or to time of eruption. These trace element features demonstrate that successive eruptions in one small area of the rift valley can show wide variations in trace element chemistry over a short span of time; they preclude the derivation of these basalt glasses from a single magma chamber. Despite the heterogeneities in REE and the variable trace element abundances, a homogeneous mantle source is suggested by the similarities among the samples in the incompatible element ratios of La/Ce, Ba/Th, Zr/Nb and K/Ba and the small range in87Sr/86Sr isotope ratios observed in other samples from the FAMOUS region (White and Bryan, 1977). Thus, trace element heterogeneities appear to be generated by processes in the mantle during melting. However, processes such as batch partial melting, fractional fusion, fractional crystallization, zone refining, or mixing of magmas or sources acting alone are incapable of explaining the lack of correlation between the light and heavy REE. It is suggested that the observed variations are a consequence of dynamic partial melting of a homogeneous mantle source region. This process includes varying degrees of partial melting of an uprising mantle source with continuous but incomplete removal of melt as melting proceeds, varying extents of batch partial melting, and zone refining. Dynamic melting can produce different melts from a homogeneous source which have different degrees of light-REE enrichment and crossing REE patterns. The variable trace element abundances which may be produced through dynamic melting may be the cause of the apparent decoupling of major and trace elements (Bryan et al., 1976) which previously has been suggested for the FAMOUS region (Bryan and Moore, 1977).

Apollo 11 igneous rock vug clinopyroxene composite crystal with tabular pigeonite nucleus and subcalcic augite precipitation

Basaltic and monomineralic fragments from the 150-425 micron size fractions of the Luna 16 core obtained from the Sea of Fertility were studied by optical petrographic, electron microprobe, and single-crystal X-ray diffraction techniques. Three textural varieties were identified in the basalts (intersertal, subophitic, and recrystallized). These textures, the assemblages, and individual mineral compositions (especially pyroxenes) indicate that these basalts crystallized under conditions very similar to those from Apollo 11. The pyroxenes have slightly lower Ti/Al (atomic) ratios than the Apollo 11 pyroxenes. We interpret the presence of octahedral Al as being due to the low TiO2/Al2O3 (weight %) ratio in the bulk rock. All observations made on the fine-grained basalt fragments are consistent with a rapid, near-surface, one-stage crystallization history.

Analysis of 'inverted pigeonites' found in Apollo 14 samples 14082 and 14083 (a polymict breccia, the 'white rock') by a combination of optical, electron probe, and single-crystal X-ray diffraction techniques. These 'inverted pigeonites' are regarded as samples of plutonic rocks that have been blasted out of the Imbrium Basin. It is also concluded that lunar pigeonites will invert to orthopyroxenes, given sufficiently slow cooling histories even in very anhydrous environments.

A total of 139 breccia and crystalline rock fragments in the size range 2–4 mm from four Apollo 15 soil samples have been examined. Two of the sample stations are on the mare surface (4 and 9A) and two are on the Apennine Front (2 and 6). Approximately 90% of the fragments from the Apennine Front are brown-glass “soil” breccias, but those from the mare surface are 60%–70% basalt. Several textural varieties of mare basalt have been recognized, but within experimental error there is no difference in their40Ar-39Ar ages. The major non-mare (Pre-Imbrian) crystalline rock types in the Apennine Front regolith are KREEP basalt, anorthositic rocks, recrystallized norite (including anorthositic norite) and recrystallized polymict breccias; however, such crystalline rocks are rare in the samples examined. Apparently, the near surface Imbrium ejecta below the regolith has not been thermally recrystallized, and probably there are no outcrops of crystalline rocks upslope from the sample stations.

Chemical and mineralogical study of Kodaikanal meteorite silicate and metal phases, using optical, X ray and electron microprobe techniques

Clinopyroxenes from Apollo 12 rocks studied by X ray diffraction and electron microprobe methods, noting phenocrysts, chemical composition and crystallization

Apollo 12 clinopyroxenes exsolution and epitaxy by electron microprobe and single crystal X ray diffraction

Only fine-grained rocks are present in the Luna 20 samples, and coarser-grained rocks are represented by fragments of single crystals. A petrologic study has been made of 47 fine-grained crystalline rocks, microbreccias, and glassy aggregates. In addition, a total of 33 single crystals of pyroxene, plagioclase, olivine, and spinel, in the size range from 125 to 500 microns, have been examined using electron microprobe and single-crystal X-ray diffraction techniques. The most abundant fine-grained crystalline rocks in the samples examined are recrystallized anorthositic norite and anorthositic troctolite. Gabbroic rocks, anorthosite, and KREEP basalt are present but not common. Most of the single crystals of pyroxene and plagioclase could have been derived from coarser-grained noritic, troctolitic, and anorthositic rocks. However, three of the 14 pyroxene crystals, and two of the five olivine crystals have Fe/(Fe + Mg) contents greater than 0.45 and are believed to have been derived from mare basalts or related rocks.